Pesticidal and parasiticidal di-and trifluorosubstituted alkene compounds

ABSTRACT

Di- and trifluorosubstituted alkene compounds of formula I  
                 
 
     wherein  
     X is hydrogen or fluorine;  
     Y is oxygen, NR 1  or S(O) m ;  
     R 1  is hydrogen or C 1 -C 6 -alkyl;  
     m is 0, 1, or 2;  
     A,B,D and E are selected from the following:  
     a) A is N and B, D and E are CR 2 ; or  
     b) B is N and A, D and E are CR 2 ; or  
     c) D is N and A, B, and E are CR 2 ; or  
     d) A and D are N and B and E are CR 2 ; or  
     e) B and E are N and A and D are CR 2 ;  
     R 2  is H, halogen, NH 2 , NO 2 , CN, alkyl, haloalkyl, alkenyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, aminosulfonyl, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl,alkylaminoalkyl, dialkylaminoalkyl, hydroxycarbonyl, or alkoxycarbonyl; or  
     phenyl which may be substituted with halogen, CN, NO 2 , alkyl, haloalkyl, alkoxy, or haloalkoxy; or  
     a 5- to 6-membered heteroaromatic ring system containing 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen, which may be substituted with halogen, CN, NO, alkyl, haloalkyl, alkoxy, or haloalkoxy;  
     n is 1, 2, 3 or 4, and  
     the agriculturally and/or physiologically tolerable salts thereof,  
     methods for the preparation of compounds I, and compositions and methods for the control of nematodes and arachnids, and for treating, controlling, preventing and protecting warm-blooded animals, fish and humans against infestation and infection by helminths, arachnids and arthropod endo- and ectoparasites.

[0001] The present invention provides di- and trifluorosubstitutedalkene compounds of formula I,

[0002] wherein

[0003] X is hydrogen or fluorine;

[0004] Y is oxygen, NR¹ or S(O)_(m);

[0005] R¹ is hydrogen or C₁-C₆-alkyl;

[0006] m is 0, 1, or 2;

[0007] A,B,D and E are selected from the following:

[0008] a) A is N and B, D and E are CR²; or

[0009] b) B is N and A, D and E are CR²; or

[0010] c) D is N and A, B, and E are CR²; or

[0011] d) A and D are N and B and E are CR²; or

[0012] e) B and E are N and A and D are CR²;

[0013] R² is hydrogen, halogen, amino, nitro, cyano, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl,C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl,aminosulfonyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl,C₁-C₆-alkylsulfinyl-C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl-C₁-C₆-alkyl,C₁-C₆-alkylamino-C₁-C₆-alkyl, di-(C₁-C₆-alkyl)amino-C₁-C₆-alkyl,C₁-C₆-hydroxycarbonyl, or C₁-C₆-alkoxycarbonyl; or

[0014] phenyl which may be substituted with any combination of 1 to 5halogen atoms, 1 or 2 cyano groups, 1 or 2 nitro groups, 1 to 3C₁-C₄-alkyl groups, 1 to 4 C₁-C₄-haloalkyl groups, 1 to 3 C₁-C₄-alkoxygroups or 1 to 3 C₁-C₄-haloalkoxy groups; or

[0015] a 5- to 6-membered heteroaromatic ring system containing 1 to 3heteroatoms selected from oxygen, sulfur and nitrogen, which may besubstituted with any combination of 1 to 5 halogen atoms, 1 or 2 cyanogroups, 1 or 2 nitro groups, 1 to 3 C₁-C₄-alkyl groups, 1 to 3C₁-C₄-haloalkyl groups, 1 to 3 C₁-C₄-alkoxy groups or 1 to 3C₁-C₄-haloalkoxy groups;

[0016] n is 1, 2, 3 or 4, and

[0017] the agriculturally and/or physiologically tolerable saltsthereof.

[0018] In EP-A 405 976, anti-ulcerative thiazolopyridine compounds aredescribed which inter alia are substituted by an optionally substitutedalkene sulfide moiety.

[0019] In EP-A 1 000 946, pesticidal 2-(substitutedthio)thiazolo-[4.5-b]-pyridine compounds are described which may carry a3,4,4-trifluoro-but-3-enyl substitutent on the thio group.

[0020] However, the pesticidal and parasiticidal activity of thecompounds known from the above literature in many cases isunsatisfactory.

[0021] It is, therefore, an object of the present invention to providecompounds having improved activity for the control of nematode andacarid pests and parasites and for the protection of growing andharvested crops from damage caused by nematode and acarid attack andinfestation.

[0022] It is a further object of this invention to provide a method fortreating, controlling, preventing and protecting warm-blooded animals,fish and humans against infestation and infection by helminths, acaridsand arthropod endo- and ectoparasites.

[0023] We have found that these objects are achieved by the di- andtri-fluorosubstituted alkene compounds of formula I. Furthermore, wehave found processes for preparing the compounds of formula I.

[0024] Contrary to the compounds disclosed in EP-A 405 976, in allcompounds of formula I a fluorosubstituted alkene moiety is bonded tothe thiazolopyridine via a heteroatom. Also, EP-A 405 976 is silent withregard to any pesticidal activity of the disclosed compounds.

[0025] The compounds of formula I differ from the compounds known fromEP-A 1 000 946 in the position of the nitrogen atom in thethiazolopyridine ring.

[0026] The present invention also provides a method for the control ofnematode or acarid pests which comprises contacting said pests or theirfood supply, habitat or breeding grounds with a pesticidally orparasiticidally effective amount of a compound of formula I.

[0027] The present invention further provides a method for theprotection of growing plants from attack or infestation by nematode oracarid pests which comprises applying to the plants, or to the soil orwater in which they are growing, a pesticidally effective amount of acompound of formula I.

[0028] The present invention also provides a method for treating,controlling, preventing and protecting warm-blooded animals, fish andhumans against infestation and infection by helminths, arachnids orarthropod endo- and ectoparasites by use of compounds of formula I.

[0029] This invention also comprises pesticidal and parasiticidalcompositions containing compounds of formula I. Compounds of formula Iand compositions containing them are especially useful for the controlof nematode pests.

[0030] In the definitions of the symbols given in the above formula,collective terms were used which generally represent the followingsubstituents:

[0031] Halogen: fluorine, chlorine, bromine and iodine;

[0032] Alkyl: saturated, straight-chain or branched hydrocarbon radicalshaving 1 to 4 or 1 to 6 carbon atoms, such as methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl,pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

[0033] Haloalkyl: straight-chain or branched alkyl groups having 1 to 4or 1 to 6 carbon atoms (as mentioned above), where some or all of thehydrogen atoms in these groups may be replaced by halogen atoms asmentioned above, for example C₁-C₂-haloalkyl, such as chloromethyl,bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl,difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl,1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

[0034] A 5- to 6-membered heteroaromatic ring system containing 1 to 3heteroatoms selected from oxygen, sulfur and nitrogen, e.g is pyridine,pyrimidine, pyrazine, pyridazine, triazine, triazole, pyrazole, pyrrole,imidazole, thiophene, furane, thiazole, isoxazole, or oxazole.

[0035] Alkylsulfinyl: straight-chain or branched alkyl groups having 1to 6 carbon atoms (as mentioned above) which are attached to theskeleton via a sulfinyl group (—SO—);

[0036] Alkylsulfonyl: straight-chain or branched alkyl groups having 1to 6 carbon atoms (as mentioned above) which are attached to theskeleton via a sulfonyl group (—SO₂—);

[0037] With respect to the intended use of the compounds of formula I,particular preference is given to the following meanings of thesubstituents, in each case on their own or in combination:

[0038] Particular preference is given to compounds of formula I whereinX is fluorine.

[0039] Preference is given to compounds of formula I wherein Y is oxygenor S(O)_(m).

[0040] Particular preference is given to compounds of formula I whereinY is S(O)_(m).

[0041] Preference is given to compounds of formula I wherein m is zeroor 2.

[0042] Particular preference is given to compounds of formula I whereinm is zero.

[0043] Preferred compounds of the invention are those of formula Iwherein A is N and B, D and E are CR²; or B is N and A, D and E are CR²;or D is N and A, B, and E are CR².

[0044] Particular preference is given to compounds of formula I whereinA is N and at least two of B, D and E are CH; or B is N and at least twoof A, D and E are CH; or D is N and at least two of A, B, and E are CH.

[0045] Particular preference is given to compounds of formula I whereinA is N and at least two of B, D and E are CH.

[0046] Preference is given to compounds of formula I wherein R² ishydrogen, halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, or C₁-C₆-alkoxycarbonyl.

[0047] Preference is given to compounds of formula I wherein n is 2 or4.

[0048] Particular preference is given to compounds of formula I whereinn is 2.

[0049] Formula I compounds which are especially useful for the controlof nematodes include2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[5,4-b]pyridine,2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[5,4-c]pyridine and2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[4,5-c]pyridine.

[0050] Particular preference is given to2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[5,4-b]pyridine.

[0051] Particular preference is given to compounds of formula I wherein

[0052] X is hydrogen or fluorine;

[0053] Y is S(O)_(m);

[0054] m is 0, 1 or 2;

[0055] n is 2 or 4;

[0056] A is N and B, D and E are CR²; or B is N and A, D and E are CR²;or D is N and A, B, and E are CR² and

[0057] R² is hydrogen, halogen, cyano, nitro, C₁-C₆-alkyl,C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, orC₁-C₆-alkoxycarbonyl.

[0058] Furthermore, particular preference is given to compounds offormula I wherein

[0059] X is fluorine;

[0060] Y is S(O)_(m);

[0061] m is 0 or 2;

[0062] n is 2;

[0063] A is N and at least two of B, D and E are CH.

[0064] Likewise, particular preference is given to compounds of formulaI wherein

[0065] X is fluorine;

[0066] Y is S;

[0067] n is 2;

[0068] A is N and at least two of B, D and E are CH.

[0069] Also, particular preference is given to compounds of formula I.1

[0070] wherein m is 0, 1, or 2; A is N and B, D and E are CH; or B is Nand A, D and E are CH; or D is N and A, B, and E are CH.

[0071] Suitable amongst agriculturally and/or physiologically tolerablesalts are especially the salts of those cations which do not adverselyaffect the pesticidal and/or parasiticidal action of the compounds I.Thus, especially suitable cations are the ions of the alkali metalsincluding sodium, potassium and lithium, of the alkaline earth metalsincluding calcium and magnesium, and of the transition metals includingmanganese, copper, iron, zinc, cobalt, lead, silver, nickel, and alsoammonium or organic ammonium including monoalkylammonium,dialkylammonium, trialkylammonium, tetraalkylammonium,monoalkenylammonium, dialkenylammonium, trialkenylammonium,monoalkynylammonium, dialkynylammonium, monoalkanolammonium,dialkanolammonium, C₅-C₆-cycloalkylammonium, piperidinium, morpholinium,pyrrolidinium, or benzylammonium, moreover phosphonium ions, sulfoniumions, preferably tri(C₁-C₄-alkyl)sulfonium and sulfoxonium ions,preferably tri(C₁-C₄-alkyl)sulfoxonium.

[0072] With respect to their use, particular preference is given to thecompounds I.2 compiled in the Tables below. Moreover, the groupsmentioned for a substituent in the Tables are on their own,independently of the combination in which they are mentioned, aparticularly preferred embodiment of the substituent in question.

[0073] Table 1

[0074] Compounds of the formula I.2 wherein R² is hydrogen, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0075] Table 2

[0076] Compounds of the formula I.2 wherein R² is methyl, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0077] Table 3

[0078] Compounds of the formula I.2 wherein R² is ethyl, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0079] Table 4

[0080] Compounds of the formula I.2 wherein R² is n-propyl., p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0081] Table 5

[0082] Compounds of the formula I.2 wherein R² is iso-propyl, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0083] Table 6

[0084] Compounds of the formula I.2 wherein R² is n-butyl, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0085] Table 7

[0086] Compounds of the formula I.2 wherein R² is iso-butyl, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0087] Table 8

[0088] Compounds of the formula I.2 wherein R² is tert-butyl, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0089] Table 9

[0090] Compounds of the formula I.2 wherein R² is fluorine, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0091] Table 10

[0092] Compounds of the formula I.2 wherein R² is chlorine, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0093] Table 11

[0094] Compounds of the formula I.2 wherein R² is bromine, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0095] Table 12

[0096] Compounds of the formula I.2 wherein R² is iodine, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0097] Table 13

[0098] Compounds of the formula I.2 wherein R² is cyano, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0099] Table 14

[0100] Compounds of the formula I.2 wherein R² is nitro, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0101] Table 15

[0102] Compounds of the formula I.2 wherein R² is methoxy, p is 1 andthe combination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0103] Table 16

[0104] Compounds of the formula I.2 wherein R² is ethoxy, p is 1 and thecombination of X, A, B and D and the position of R² for a compoundcorresponds in each case to a row of Table A.

[0105] Table 17

[0106] Compounds of the formula I.2 wherein R² is methoxycarbonyl, p is1 and the combination of X, A, B and D and the position of R² for acompound corresponds in each case to a row of Table A.

[0107] Table 18

[0108] Compounds of the formula I.2 wherein R² is trifluoromethyl, p is1 and the combination of X, A, B and D and the position of R² for acompound corresponds in each case to a row of Table A.

[0109] Table 19

[0110] Compounds of the formula I.2 wherein R² is trifluoromethoxy, p is1 and the combination of X, A, B and D and the position of R² for acompound corresponds in each case to a row of Table A. TABLE A Nr. X A BD Position of R² A-1 H N CH CH 4 A-2 H N CH CR² 5 A-3 H N CR² CH 6 A-4 FN CH CH 4 A-5 F N CH CR² 5 A-6 F N CR² CH 6 A-7 H CH N CH 4 A-8 H CH NCR² 5 A-9 H CR² N CH 7 A-10 F CH N CH 4 A-11 F CH N CR² 5 A-12 F CR² NCH 7 A-13 H CH CH N 4 A-14 H CH CR² N 6 A-15 H CR² CH N 7 A-16 F CH CH N4 A-17 F CH CR² N 6 A-18 F CR² CH N 7

[0111] Compounds of formula Ia

[0112] wherein X, A, B, D, E, and n are as defined for formula I, reobtainable by reaction of compounds of formula II

[0113] wherein A, B, D, and E are as defined for formula I, withcompounds of formula III

L-(CH₂)_(n)—CX═CF₂  (III)

[0114] wherein X and n are as defined for formula I and L is anucleophilic exchangeable leaving group, preferably halogen such asbromine.

[0115] The reaction is usually carried out at temperatures of from 0° C.to 150° C., preferably from 15° C. to 80° C., in an inert organicsolvent in the presence of a base.

[0116] Suitable solvents are halogenated hydrocarbons, such as methylenechloride and chlorobenzene, ethers, such as dimethylether, digylme,dioxane and tetrahydrofuran, nitriles, such as acetonitrile, ketones,such as acetone, and also dimethyl sulfoxide, dimethyl formamide anddimethyl acetamide. Preferred solvents are acetone and dimethylformamide. It is also possible to use mixtures of the solventsmentioned.

[0117] Suitable bases are inorganic compounds, such as alkali metal andalkaline earth metal carbonates, such as lithium carbonate, potassiumcarbonate and calcium carbonate, alkali metal bicarbonates, such assodium bicarbonate, and also organic bases, for example tertiary amines,such as trimethyl amine, triethyl amine, tri-isopropyl ethyl amine undN-methyl-piperidine, and pyridine. Particular preference is given toalkaline earth metal carbonates, especially potassium carbonate.

[0118] In general, the base is employed in equimolar amounts or inexcess.

[0119] The starting materials are generally reacted with one another inequimolar amounts. In terms of yield, it may be advantageous to use anexcess of compounds of formula III based on compounds II.

[0120] Heterocyclic thiols of formula II are known or are commerciallyavailable, or they can be prepared by known methods [see e.g. Synthesis3, 358-360 (2001)].

[0121] Compounds of formula III are known from the literature or arecommercially available [see e.g. WO 86/07590 and WO 95/24403].

[0122] Sulfinyl and sulfonyl compounds of formula I wherein m is 1 or 2may be prepared by oxidizing compounds of formula I wherein m is 0. Theoxidation is usually carried out at temperatures of from (−10)° C. to150° C., preferably from 0° C. to 60° C., in an inert organic solvent orwater. Suitable oxidizing agents are, for example m-chloroperbenzoicacid, peracetic acid, H₂O₂×BF₃, K₂S₂O₇/H₂SO₄, peroxytrifluoroaceticacid, or hydrogen peroxide, optionally in combination with catalyticamounts of sodium tungsten dihydrate.

[0123] Suitable solvents are halogenated hydrocarbons, such as methylenechloride and chloroform alcohols, such as methanol and tert.-butanol,carboxylic acids such as acetic acid and trifluoroacetic acid, and alsodimethyl sulfoxide, dimethyl formamide and dimethyl acetamide. Preferredsolvents are methylene chloride and acetic acid. It is also possible touse mixtures of the solvents mentioned.

[0124] Compounds of formula I wherein X, A, B, D, E, and n are asdefined for formula I and Y is OH or NH₂ are obtainable in a similarmanner as described above for compounds of formula Ia wherein Y is S byreaction of compounds of formulae IV or V or their tautomers

[0125] wherein A, B, D, and E are as defined for formula I, withcompounds of formula III

L-(CH₂)_(n)—CX═CF₂  (III)

[0126] wherein X and n are as defined for formula I and L is anucleophilic exchangeable leaving group, preferably halogen such asbromine.

[0127] The reaction is usually carried out at temperatures of from 0° C.to 150° C., preferably from 20° C. to 120° C., in an inert organicsolvent in the presence of a base.

[0128] Suitable solvents are halogenated hydrocarbons, such as methylenechloride and chlorobenzene, ethers, such as dimethylether, digylme,dioxane and tetrahydrofuran, nitriles, such as acetonitrile, ketones,such as acetone, and also dimethyl sulfoxide, dimethyl formamide anddimethyl acetamide. Preferred solvents are acetone and dimethylformamide. It is also possible to use mixtures of the solventsmentioned.

[0129] Suitable bases are inorganic compounds, such as alkali metal andalkaline earth metal carbonates, such as lithium carbonate, potassiumcarbonate and calcium carbonate, alkali metal bicarbonates, such assodium bicarbonate, and also organic bases, such as tertiary amines,such as trimethyl amine, triethyl amine, tri-isopropyl ethyl amine undN-methyl-piperidine, and pyridine. Particular preference is given toalkaline earth metal carbonates, especially potassium carbonate.

[0130] In general, the base is employed in equimolar amounts or inexcess.

[0131] The starting materials are generally reacted with one another inequimolar amounts. In terms of yield, it may be advantageous to use anexcess of compounds of formula III based on compounds II.

[0132] Heterocyclic thiols of formula IV or V are known or can beprepared by known methods [see Heterocycles, 36, 133-144 (1993);Monatsh. Chem. 119, 333-339 (1989)].

[0133] The reaction mixtures are worked up in a customary manner, forexample by mixing with water, phase separation and, if appropriate,chromatographic purification of the crude products. In some cases, theintermediates and end products are obtained in the form of colorless orpale brown viscous oils, which are purified or freed from volatilecomponents under reduced pressure and at moderately elevatedtemperature. If the intermediates and end products are obtained assolids, they can also be purified by recrystallization or digestion.

[0134] If individual compounds I are not obtainable by the routedescribed above, they can be prepared by derivatization of othercompounds I.

[0135] Agriculturally and/or physiologically tolerable salts of thecompounds I can be formed in a customary manner, e.g. by reaction with abase of the cation in question, preferably an alkali metal hydroxide oralkali metal hydride.

[0136] The formula I compounds of this invention are useful for thecontrol of nematodes, especially plant parasitic nematodes such as rootknot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, and other Meloidogyne species; cyst-forming nematodes,Globodera rostochiensis and other Globodera species; Heterodera avenae,Heterodera glycines, Heterodera schachtii, Heterodera trifolii, andother Heterodera species; Seed gall nematodes, Anguina species; Stem andfoliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimuslongicaudatus and other Belonolaimus species; Pine nematodes,Bursaphelenchus xylophilus and other Bursaphelenchus species; Ringnematodes, Criconema species, Criconemella species, Criconemoidesspecies, Mesocriconema species; Stem and bulb nematodes, Ditylenchusdestructor, Ditylenchus dipsaci and other Ditylenchus species; Awlnematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchusmulticinctus and other Helicotylenchus species; Sheath and sheathoidnematodes, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species; Lance nematodes, Hoploaimus species; falserootknot nematodes, Nacobbus species; Needle nematodes, Longidoruselongatus and other Longidorus species; Pin nematodes, Paratylenchusspecies; Lesion nematodes, Pratylenchus neglectus, Pratylenchuspenetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and otherPratylenchus species; Burrowing nematodes, Radopholus similis and otherRadopholus species; Reniform nematodes, Rotylenchus robustus and otherRotylenchus species; Scutellonema species; Stubby root nematodes,Trichodorus primitivus and other Trichodorus species, Paratrichodorusspecies; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchusdubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulusspecies; Dagger nematodes, Xiphinema species; and other plant parasiticnematode species.

[0137] The compounds of formula I are also useful for controlling insectand/or acarid pests, preferably acarid pests. Pests controlled by theformula I compounds of this invention include those from the orderLepidoptera, Coleoptera, Diptera, Thysanoptera, Hymenoptera,Heteroptera, Homoptera, Isoptera, Orthoptera, and Acarina.

[0138] The compounds I also are suitable for use as fungicides. Theyexhibit activity against a broad spectrum of phytopathogenic fungi, inparticular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them act systemically, and theycan be employed in crop protection as foliar- and soil-actingfungicides.

[0139] Compounds of formula I are suitable for use as herbicides.Depending upon the application method, compounds I and herbicidalcompositions comprising them may be used in crops for the control ofunwanted plants. Compounds of formula I may also be used in crops thathave acquired resistance against other herbicides.

[0140] The compounds of formula I are especially useful for the controlof nematodes.

[0141] In practice generally about 0.1 ppm to about 10,000 ppm andpreferably about 1 ppm to about 5,000 ppm of a formula I compound,dispersed in water or another liquid carrier, is effective when appliedto plants or the soil or water in which the plants are growing or are tobe grown to protect the plants from nematode, insect and/or acaridattack and infestation.

[0142] The di- or tri-fluorosubstituted compounds are also effective forcontrolling nematode, insect and/or acarid pests when applied to thepests or to their food supply, habitat or breeding ground or forprotecting plants from attack or infestation by the pests when appliedto the foliage, stem or roots of the plants and/or to the soil or waterin which said plants are growing or are to be grown in sufficient amountto provide a rate of about 0.01 kg/ha to 100 kg/ha, preferably fromabout 0.1 to about 3.0 kg/ha, of active ingredient.

[0143] While the formula I compounds of this invention are effective forcontrolling nematode, insect and/or acarid pests of agronomic crops,both growing and harvested, when employed alone, they may also be usedin combination with other biological agents used in agriculture,including other nematicides, insecticides and/or acaricides. Mixing thecompounds I or the compositions comprising them in the use form aspesticides with other pesticides frequently results in a broaderpesticidal spectrum of action. For example, the formula I compounds ofthis invention may be used effectively in conjunction or combinationwith pyrethroids, phosphates, carbamates, cyclodienes, formamidines,phenol tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas,pyrroles and the like. The following list of pesticides together withwhich the compounds according to the invention can be used, is intendedto illustrate the possible combinations by way of example.

[0144] Organophosphates: Acephate, Azinphos-methyl, Chlorpyrifos,Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate,Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion,Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos,oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet,Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos,Prothiofos, Sulprophos, Triazophos, Trichlorfon;

[0145] Carbamates: Alanycarb, Benfuracarb, Carbaryl, Carbosulfan,Fenoxycarb, Furathiocarb, Indoxacarb, Methiocarb, Methomyl, oxamyl,Pirimicarb, Propoxur, Thiodicarb, Triazamate;

[0146] Pyrethroids: Bifenthrin, Cyfluthrin, Cypermethrin, Deltamethrin,Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin,Lambda-Cyhalothrin, Permethrin, Silafluofen, Tau-Fluvalinate,Tefluthrin, Tralomethrin, Zeta-Cypermethrin;

[0147] Arthropod growth regulators: a) chitin synthesis inhibitors:benzoylureas: Chlorfluazuron, Diflubenzuron, Flucycloxuron,Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron,Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole,Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide,Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d)lipid biosynthesis inhibitors: Spirodiclofen;

[0148] Various: Abamectin, Acequinocyl, Amitraz, Azadirachtin,Bifenazate, Cartap, Chlorfenapyr, Chlordimeform, Cyromazine,Diafenthiuron, Dinetofuran, Diofenolan, Emamectin, Endosulfan, Endotoxinof Bacillus thuringiensis (Bt), Fenazaquin, Fipronil, Formetanate,Formetanate Hydrochloride, Hydramethylnon, Imidacloprid, Indoxacarb,Pyridaben, Pymetrozine, Spinosad, Sulfur, Tebufenpyrad, Thiamethoxam,and Thiocyclam.

[0149] The compounds I can be converted into the customary formulations,e.g. solutions, emulsions, microemulsions, suspensions, flowableconcentrates, dusts, powders, pastes and granules. The use form dependson the particular purpose; in any case, it should guarantee a fine anduniform distribution of the compound according to the invention.

[0150] The formulations are prepared in a known manner, e.g. byextending the active ingredient with solvents and/or carriers, ifdesired using emulsifiers and dispersants, it also being possible to useother organic solvents as auxiliary solvents if water is used as thediluent. Auxiliaries which are suitable are essentially: solvents suchas aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol,butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.highly-disperse silica, silicates); emulsifiers such as non-ionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

[0151] Suitable surfactants are alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcoholsulfates and fatty acids and their alkali metal and alkaline earth metalsalts, salts of sulfated fatty alcohol glycol ether, condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of napthalenesulfonic acid with phenol orformaldehyde, polyoxyethylene octylphenyl ether, ethoxylatedisooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers,tributylphenyl polyglycol ethers, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignin-sulfite waste liquors and methylcellulose.

[0152] Substances which are suitable for the preparation of directlysprayable solutions, emulsions, pastes or oil dispersions are mineraloil fractions of medium to high boiling point, such as kerosene ordiesel oil, furthermore coal tar oils and oils of vegetable or animalorigin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene,toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenesor their derivatives, methanol, ethanol, propanol, butanol, chloroform,carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene,isophorone, strongly polar solvents, e.g. dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and water.

[0153] Powders, materials for scattering and dusts can be prepared bymixing or concomitantly grinding the active substances with a solidcarrier.

[0154] Granules, e.g. coated granules, compacted granules, impregnatedgranules and homogeneous granules, can be prepared by binding the activeingredients to solid carriers. Examples of solid carriers are mineralearths, such as silicas, silica gels, silicates, talc, kaolin, attaclay,limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground syntheticmaterials, fertilizers, e.g. ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

[0155] Such formulations or compositions of the present inventioninclude a formula I compound of this invention (or combinations thereof)admixed with one or more agronomically acceptable inert, solid or liquidcarriers. Those compositions contain a pesticidally effective amount ofsaid compound or compounds, which amount may vary depending upon theparticular compound, target pest, and method of use.

[0156] In general, the formulations comprise of from 0.01 to 95% byweight, preferably from 0.1 to 90% by weight, of the active ingredient.The active ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

[0157] The following are exemplary formulations:

[0158] I. 5 parts by weight of a compound according to the invention aremixed intimately with 95 parts by weight of finely divided kaolin. Thisgives a dust which comprises 5% by weight of the active ingredient.

[0159] II. 30 parts by weight of a compound according to the inventionare mixed intimately with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which had been sprayedonto the surface of this silica gel. This gives a formulation of theactive ingredient with good adhesion properties (comprises 23% by weightof active ingredient).

[0160] III. 10 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 90 parts by weight of xylene, 6parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 molof oleic acid N-monoethanolamide, 2 parts by weight of calciumdodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol ofethylene oxide and 1 mol of castor oil (comprises 9% by weight of activeingredient).

[0161] IV. 20 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 60 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight ofthe adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 5parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol ofcastor oil (comprises 16% by weight of active ingredient).

[0162] V. 80 parts by weight of a compound according to the inventionare mixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill (comprises 80% by weight of active ingredient).

[0163] VI. 90 parts by weight of a compound according to the inventionare mixed with 10 parts by weight of N-methyl-α-pyrrolidone, which givesa solution which is suitable for use in the form of microdrops(comprises 90% by weight of active ingredient).

[0164] VII. 20 parts by weight of a compound according to the inventionare dissolved in a mixture composed of 40 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight ofthe adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol ofcastor oil. Pouring the solution into 100,000 parts by weight of waterand finely distributing it therein gives an aqueous dispersion whichcomprises 0.02% by weight of the active ingredient.

[0165] VIII. 20 parts by weight of a compound according to the inventionare mixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of the activeingredient.

[0166] The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, e.g. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, scattering orpouring. The use forms depend entirely on the intended purposes; in anycase, this is intended to guarantee the finest possible distribution ofthe active ingredients according to the invention.

[0167] Aqueous use forms can be prepared from emulsion concentrates,pastes or wettable powders (sprayable powders, oil dispersions) byadding water. To prepare emulsions, pastes or oil dispersions, thesubstances as such or dissolved in an oil or solvent, can be homogenizedin water by means of wetter, tackifier, dispersant or emulsifier.Alternatively, it is possible to prepare concentrates composed of activesubstance, wetter, tackifier, dispersant or emulsifier and, ifappropriate, solvent or oil, and such concentrates are suitable fordilution with water.

[0168] The active ingredient concentrations in the ready-to-use productscan be varied within substantial ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

[0169] The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even the activeingredient without additives.

[0170] Various types of oils, herbicides, fungicides, other pesticides,or bactericides may be added to the active ingredients, if appropriatealso only immediately prior to use (tank mix). These agents can beadmixed with the agents according to the invention in a weight ratio of1:10 to 10:1.

[0171] This invention also provides a method for treating, curing,controlling, preventing and protecting warm-blooded animals, includinghumans, and fish against infestation and infection by helminths,arachnids and arthropod endo- and ectoparasites which comprises orally,topically or parenterally administering or applying to said animals ananthelmintically, acaricidally or endo- or ectoparasiticidally effectiveamount of di- or tri-fluorosubstituted compound of formula I.

[0172] The above method is particularly useful for controlling andpreventing helminth, nemtode, acarid and arthropod endo- andectoparasitic infestations and infections in warm-blooded animals suchas cattle, sheep, swine, camels, deer, horses, poultry, fish, rabbits,goats, mink, fox, chinchillas, dogs and cats as well as humans.

[0173] In the context of control and prevention of infestation andinfections in warm-blooded animals, compounds of formula I areespecially useful for the control of helminths and nematodes. Examplesfor helminths are members of the class Trematoda, commonly known asflukes or flatworms, especially members of the genera Fasciola,Fascioloides, Paramphistomum, Dicrocoelium, Eurytrema, Ophisthorchis,Fasciolopsis, Echinostoma and Paragonimus. Nematodes which can becontrolled by the formula I compounds include the genera Haemonchus,Ostertagia, Cooperia, Oesphagastomum, Nematodirus, Dictyocaulus,Trichuris, Dirofilaria, Ancyclostoma, Ascaria and the like.

[0174] The formula I compounds of this invention also controlendoparasitic arthropod infestations such as cattle grub and stomachbot. In addition, acarid and arthropod ectoparasitic infestations inwarm-blooded animals and fish including biting lice, sucking lice, botflies, biting flies, muscoid flies, flies, myiasitic fly larvae, gnats,mosquitoes, fleas, mites, ticks, nasal bots, keds and chiggers may becontrolled, prevented or eliminated by the compounds of this invention.Biting lice include members of Mallophaga such as Bovicola bovis,Trichodectes canis and Damilina ovis. Sucking lice include members ofAnoplura such as Haematopinus eurysternus, Haematopinus suis,Linognathus vituli and Solenopotes capillatus. Biting flies includemembers of Haematobia. Ticks include Boophilus, Rhipicephalus, Ixodes,Hyalomma, Amblyomma and Dermacentor. The formula I compounds may also beused to control mites which are parasitic on warm-blooded mammals andpoultry including mites of the orders Acariformes and Parasitiformes.

[0175] For oral administration to warm-blooded animals, the formula Icompounds may be formulated as animal feeds, animal feed premixes,animal feed concentrates, pills, solutions, pastes, suspensions,drenches, gels, tablets, boluses and capsules. In addition, the formulaI compounds may be administered to the animals in their drinking water.For oral administration, the dosage form chosen should provide theanimal with about 0.01 mg/kg to 100 mg/kg of animal body weight per dayof the formula I compound.

[0176] Alternatively, the formula I compounds may be administered toanimals parenterally, for example, by intraruminal, intramuscular,intravenous or subcutaneous injection. The formula I compounds may bedispersed or dissolved in a physiologically acceptable carrier forsubcutaneous injection. Alternatively, the formula I compounds may beformulated into an implant for subcutaneous administration. In additionthe formula I compound may be transdermally administered to animals. Forparenteral administration, the dosage form chosen should provide theanimal with about 0.01 mg/kg to 100 mg/kg of animal body weight per dayof the formula I compound.

[0177] The formula I compounds may also be applied topically to theanimals in the form of dips, dusts, powders, collars, medallions, spraysand pour-on formulations. For topical application, dips and spraysusually contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to3,000 ppm of the formula I compound. In addition, the formula Icompounds may be formulated as ear tags for animals, particularlyquadrupeds such as cattle and sheep.

[0178] The formula I compounds of this invention may also be used incombination or conjunction with one or more other parasiticidalcompounds including, but not limited to, anthelmintics, such asbenzimidazoles, piperazine, levamisole, pyrantel, praziquantel and thelike; endectocides such as avermectins, milbemycins and the like;ectoparasiticides such as arylpyrroles, organophosphates, carbamates,gamabutyric acid inhibitors including fipronil, pyrethroids, spinosads,imidacloprid and the like; insect growth regulators such aspyriproxyfen, cyromazine and the like; and chitin synthase inhibitorssuch as benzoylureas including flufenoxuron.

[0179] The formula I compounds may also be used in combination orconjunction with one or more compounds selected from piperonyl butoxide,N-octyl bicycloheptene dicarboximide, dipropylpyridine-2,5-dicarboxylate and1,5a,6,9,9a,9b-hexahydro-4a(4H)-dibenzofurancarboxaldehyde to broadenthe spectrum of activity.

[0180] The parasiticidal compositions of the present invention include aparasiticidally effective amount of a formula I compound of thisinvention or combinations thereof admixed with one or more agronomicallyacceptable and/or physiologically tolerable inert, solid or liquidcarriers known from veterinary medicinal practice for oral, percutaneousand topical administration. Such compositions may comprise furtheradditives, such as stabilizers, anifoams, viscosity regulators, bindersand tackifiers. Whereas commercial products will preferably beformulated as concentrates, the end user will normally employ diluteformulations.

SYNTHESIS EXAMPLES

[0181] The compounds I obtained according to the protocols shown in thesynthesis examples below together with their physical data are listed inTable I which follows.

Example 1

[0182] Preparation of2-(3,4,4-Trifluoro-but-3-enylsulfanyl)-thiazolo[5,4-b]pyridine

[0183] A solution of thiazolo[5,4-b]pyridine-2-thiol (6.2 g) inN,N-diethyl formamide under nitrogen was treated with1,1,2-trifluoro-4-bromobutene (8.3 g) and potassium carbonate (1.5 g),stirred at 60° C. for 24 hours, cooled, and poured into water. Theresultant aqueous mixture was extracted with diethyl ether. The organicextract was dried over anhydrous sodium sulfate and concentrated invacuo to obtain a residue. Column chromatography of the residue usingsilica gel and a 9:1 hexanes/ethyl acetate solution gave the titleproduct as a colorless oil (8.9 g).

[0184] Elemental analysis: C₁₀H₇F₃N₂S₂

[0185] Calculated: C, 43.47; H, 2.55; N, 10.14%.

[0186] Found: C, 43.46; H, 2.58; N, 10.14%.

Example 2

[0187] Preparation of2-(3,4,4-trifluoro-4-but-3-enylsulfanyl)-thiazolo[5,4-c]pyridine

[0188] A. 2-Thio-[5,4c]thiazolopyridine O-Ethylxanthic acid potassiumsalt (1.52 g) was added to a solution of 3-chloro-4-aminopyridine inN-methylpyrrolidinone (6 ml) and the mixture was heated at reflux for 4hours, cooled to room temperature and diluted with water (30 ml). Themixture was acidified with acetic acid and filtered to give the productas a brown solid (0.68 g).

[0189] B.2-(3,4,4-Trifluoro-4-but-3-enylsulfanyl)-thiazolo[5,4-c]pyridine

[0190] Potassium carbonate was added to a solution of thethiazolopyridine, prepared in Step A, (0.55 g) in dimethylformamide (8ml) and the mixture was heated at 70° C. for 20 min. The mixture wascooled to room temperature and a solution of4-bromo-1,1,2-trifluoro-1-butene on dimethylformamide (2 ml) was added.The mixture was stirred at room temperature 2 hours, diluted with water(50 ml) and extracted with ethyl acetate. The organic fraction waswashed with water and saturated brine, dried over magnesium sulfate,filtered and evaporated. The residue was chromatographed on silica gelusing ethyl acetate:hexanes (4:3) to give the product as a brown oil(0.55 g).

Example 3

[0191] Preparation of2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[4,5c]pyridine

[0192] A. 2-Thio-[4,5-c]-thiazolopyridine

[0193] O-Ethylxanthic acid potassium salt (5 g) was added to4-chloro-3-aminopyridine (2 g) in N-methylpyrrolidinone (20 ml), heatedat reflux for 4 hours, cooled to room temperature and diluted with water(50 ml). The solution was acidified with acetic acid to pH and filteredto give 2.35 g of the product as a gray solid of mp. =>220° C.

[0194] B. 2-(3,4,4-Trifluoro-but-3-enylsulfanyl)-thiazolo[4,5c]pyridine

[0195] Potassium carbonate (1.9 g) was added to a solution of thethiazolopyridine (2.1 g) prepared in step 1 in dimethylformamide (30ml). The mixture was heated at 70° C. for 25 min and cooled to roomtemperature. A solution of 4-bromo-1,1,2-trifluoro-1-butene indimethylformamide (3 ml) was added and the mixture was stirred overnightat room temperature. The reaction mixture was poured into water (100 ml)and saturated aqueous sodium chloride solution (20 ml) and extractedwith ethyl acetate. The organic extracts were washed with water andbrine, dried over magnesium sulfate, filtered and evaporated. Theresidue was chromatographed on silica gel using ethyl acetate/hexanes(3/2) to give the product as a brown oil (3.16 g).

Example 4

[0196] 40 Preparation of2-(3,4,4-trifluoro-but-3-enylsulfinyl)-thiazolo[4,5-c]pyridine

[0197] To a solution of2-(3,4,4-trifluoro-but-3-enylsulfanyl)-thiazolo[4,5c]pyridine (2.14 g)in methylene chloride (150 ml) there was added m-chloroperbenzoic acid(2.56 g) and the solution mixture was stirred for 30 min, after whichthe solvent was evaporated. The residue was dissolved in ethyl acetate(100 ml) and washed with 1% aqueous sodium chloride, dired overmagnesium sulfate, filtered and evaporated. The residue waschromatographed on silica gel using hexane:ethyl acetate (7:3) to givethe product as a white solid (0.8 g).

Example 5

[0198] Preparation of2-(3,4,4-trifluoro-but-3-enylsulfonyl)-thiazolo[4,5-c]pyridine

[0199] 2-(3,4,4-trifluoro-but-3-enylsulfinyl)-thiazolo[4,5-c]pyridine(0.1 g) was dissolved in methylene chloride (5 ml), m-chloroperbenzoicacid (0.07 g) was added and the mixture was stirred at room temperaturefor 2 hours. The mixture was washed with 1% aqueous sodiummetabisulfite, aqueous sodium bicarbonate, saturated aqueous sodiumchloride, dried over magnesium sulfate, filtered and evaporated. Theresidue was chromatographed on silica gel using methylene chloride:ethylacetate (85:15) to give the product as a brown semi-solid (0.05 g).TABLE I (I.1)

Physical data: No. A B D E m ¹H-NMR (δ [ppm]) 1.1-1 N CH CH CH 02.85(m_(c)), 3.55(t), 7.35(m_(c)), 8.05(d), 8.45(m_(c)). 1.1-2 N CH CHCH 1 2.70(m_(c)), 3.00(m_(c)), 3.50(m_(c)), 7.55(m_(c)), 8.35(d),8.70(d). 1.1-3 N CH CH CH 2 3.00(m_(c)), 3.75(t), 7.65(m_(c)), 8.50(d),8.80(d). 1.1-4 N OCH₃ CH CH 0 2.85(m_(c)), 3.55(t), 4.00(s), 6.80(d),7.95(d).

[0200] Examples of Action Against Animal Pests

[0201] The action of the compounds of the formula I against pests wasdemonstrated by the following experiments:

[0202] Activity Against Nematode Plant Diseases

[0203] Soil nematicide assay targeting root-knot nematode Meloidogyneincognita on tomato

[0204] The test compounds were solubilized in acetone and diluted withwater and surfactant to the required test concentrations. The testsolution was applied as a soil drench to transplanted tomato plants incells with sandy loam mixed with sand. One thousand root-knot J2 larvaewere applied as an aqueous suspension drenched on the soil surface. Theplants were maintained in the greenhouse and, one month afterinoculation, the plant roots were washed free of soil. The root-knotgalls on the root system of each plant were counted. Treatments werereplicated three times. Percent control of root-knot was calculated forthe treated plants relative to control plants treated with theacetone-surfactant carrier using the following formula:

% control of root knot galls=100×((median number of galls on controlplants−median number of galls on treated plants)/median number of gallson control plants)

[0205] In this test, compound A which is known from EP-A 1 000 946 asexample 1 acted as comparison active ingredient.

[0206] In this experiment, compound I.1-1 when applied at 0.63 kg/ha and0.16 kg/ha, respectively, provided 100% and 94% control of root-knotwhile the comparison compound A provided 71% and 13% control at thosesame two concentrations.

[0207] Soil nematicide assay targeting root-knot nematode Meloidogyne spon tomato

[0208] The test compounds were applied as granular formulations of 5%active ingredient on a gypsum carrier to soil infested with root-knotnematodes. Tomato plants were transplanted into the soil. After gallingdeveloped in untreated control plants, tomato plants were harvested andthe roots assessed for root knot galling. Based on visual estimation,the percentage of the tomato root-mass that was galled was determined.Percent control root-knot was calculated for the treated plants relativeto untreated control plants using the following formula:

% control of root knot galling=100×((galling level of untreatedplants−galling level of treated plants)/galling level of untreatedplants)

[0209] In this test, compound A which is known from EP-A 1 000 946 asexample 1 acted as comparison active ingredient.

[0210] In this experiment, tomato plants that had been treated with 1kg/ha of compound I.1-1 provided control of root knot galling of 47%,while the comparison compound A provided control of 25%.

[0211] Evaluation of Test Compounds Against C. elegans

[0212] Cultures of C. elegans (Bristol strain from J. Lewis) aremaintained on E. coli lawns on NG Agar Plates at 20° C. Nematodes fortesting are washed from cultures using Na buffer. Compounds aredissolved in 80% acetone. The test material is micropipetted (25 ml)into a single well of a 96-well sterile tissue culture plate and thesolvent allowed to evaporate. A freshly prepared volume (50 ml) of C.elegans in Na buffer is micropipetted into each treated well and severalcontrol wells per plate. Plates are incubated at 20° C. Observations forefficacy are made under a dissecting microscope at 4 and 24 hourspost-immersion. Activity is judged visually and semi-quantitatively,based on the drug effects on motility of the adults and larvae.

[0213] Activity Against Arachnids

[0214] Compounds were formulated as a 10.000 ppm solution in a mixtureof 35% acetone and water, which was diluted with water, if needed.Tetranychus urticae (OP-resistant strain), 2-spotted spider mite (TSM)

[0215] Sieva lima bean plants with primary leaves expanded to 7-8 cmwere infested by placing on each a small piece from an infested leaf(with about 100 mites) taken from the main colony. This was done atabout 2 hours before treatment to allow the mites to move over to thetest plant to lay eggs. The piece of leaf used to transfer the mites wasremoved. The newly-infested plants were dipped in the test solution andallowed to dry. After 2 days, one leaf is removed and mortality countsare made.

1. Di- and trifluorosubstituted alkene compounds of formula I

wherein X is hydrogen or fluorine; Y is oxygen, NR¹ or S(O)_(m); R¹ ishydrogen or C₁-C₆-alkyl; m is 0, 1, or 2; A,B,D and E are selected fromthe following: a) A is N and B, D and E are CR²; or b) B is N and A, Dand E are CR²; or c) D is N and A, B, and E are CR²; or d) A and D are Nand B and E are CR²; or e) B and E are N and A and D are CR²; R² ishydrogen, halogen, amino, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkenyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio,C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl,C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, aminosulfonyl,C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl,C₁-C₆-alkylsulfinyl-C₁-C₆-alkyl, C₁-C₆-alkylsulfonyl-C₁-C₆-alkyl,C₁-C₆-alkylamino-C₁-C₆-alkyl, di-(C₁-C₆-alkyl)amino-C₁-C₆-alkyl,C₁-C₆-hydroxycarbonyl, or C₁-C₆-alkoxycarbonyl; or phenyl which may besubstituted with any combination of 1 to 5 halogen atoms, 1 or 2 cyanogroups, 1 or 2 nitro groups, 1 to 3 C₁-C₄-alkyl groups, 1 to 4C₁-C₄-haloalkyl groups, 1 to 3 C₁-C₄-alkoxy groups or 1 to 3C₁-C₄-haloalkoxy groups; or a 5- to 6-membered heteroaromatic ringsystem containing 1 to 3 heteroatoms selected from oxygen, sulfur andnitrogen, which may be substituted with any combination of 1 to 5halogen atoms, 1 or 2 cyano groups, 1 or 2 nitro groups, 1 to 3C₁-C₄-alkyl groups, 1 to 3 C₁-C₄-haloalkyl groups, 1 to 3 C₁-C₄-alkoxygroups or 1 to 3 C₁-C₄-haloalkoxy groups; n is 1, 2, 3 or 4, and theagriculturally and/or physiologically tolerable salts thereof. 2.Compounds of formula I according to claim 1 wherein X is flourine.
 3. Aprocess for the preparation of compounds of formula Ia

wherein X, A, B, D, E, and n are as defined in claim 1, characterized inthat compounds of formula II

wherein A, B, D, and E are as defined for formula I in claim 1 arereacted with compounds of formula III L-(CH₂)_(n)—CX═CF₂  (III) whereinX and n are as defined for formula I in claim 1 and L is a nucleophilicexchangeable leaving group.
 4. The use of a compound of formula I asdefined in claims 1 or 2 for the control of nematodes or arachnids.
 5. Amethod for the control of nematodes or arachnids which comprisescontacting said pests or their food supply, habitat or breeding groundwith a pesticidally effective amount of a compound of formula I asdefined in claims 1 or
 2. 6. A method for the protection of plants frominfestation or attack by nematodes or arachnids which comprises applyingto the plants or to the soil or the water in which they are growing apesticidally effective amount of a compound of formula I as defined inclaims 1 or
 2. 7. A method for treating, controlling, preventing orprotecting warm-blooded animals or fish against infestation or infectionby helminths, arachnids or arthrop endo- or ectoparasites whichcomprises orally, topically or parenterally administering or applying tosaid animal or fish a parasiticidally effective amount of a compound offormula I as defined in claims 1 or
 2. 8. A method for the preparationof a composition for treating, controlling, preventing or protectingwarm-blooded animals or fish against infestation or infection byhelminths, arachnids or arthrop endo- or ectoparasites which comprises acompound of formula I as defined in claims 1 or
 2. 9. A composition forthe control of nematodes or arachnids which comprises an agronomicallyacceptable and/or physiologically tolerable carrier and a compound offormula I as defined in claims 1 or
 2. 10. A composition for the controlof nematodes which comprises an agronomically acceptable and/orphysiologically tolerable carrier and a compound of formula I as definedin claims 1 or 2.